Method of producing photograph dyestuff pictures



Patented Nov. 19, 1940 UNITED STATES PATENT OF F lCE mm W9 BllGlDiflHWClllf.

m Drawing. Application May is, 1939, set-mien. 214,035. In GreatBrltain May n, use

11 Claims, (01. 95-6) ters Patent No. 2,020,775 dated November 12,-

When performing the dye destruction with the hitherto known treating solutions a relatively long treating time is required which sometimes causes a deficiency in the pictures, possibly dueto the fact that the dyestufl spreads or .difluses during the extended time which the picture must remainin the treating solutions. Apart .irom the lack of definition of the picture, thus obtained, prolonged treating times are furthermore objec- 20 tionable in view of the possibility that the gelatine or other binding agent may, to a certain degree, be attacked by the dyestufi destroying solutions. Accordingly, attempts have been.

made to improve the process by shortening the time of treatment. It has been found that it is not always possible to raise the-temperature of the treating solutions and thereby to decrease the duration of the process. It has.been found, however, that the appearance of the pictures can be improved to a remarkable degree by the use of special dye destroying solutions which act in a much shorter time than those used heretofore in the process.

According to the present invention photographic pictures which comprisea developed silver image in a layer positioned immediately ad jacent to a colloid layer containing a dyestufi which is resistant to the ordinary photographic treating solutions, but which can be locally destroyed under the influence of a metallic silver image, are treatedwith dyestufl-destroying solutions which are capable of. destroying such a dyestufl under the influence or the metallic silver and which in addition contain a substance which acceleratesv the reaction between thesilver and the dyestufl.

- Typical examples of solutions which are capable of destroying the dyestuflunder the influence of a metallic silver picture and which in the absence of silver do not attack the .dyestufl' are as follows: solutions of thiocarbamide or of hy-- drohalic acids, acid solutions of guanidine or its derivatives, etc. These treating" solutions are,

.Gaspar.

according to the invention, employed with theaddition of acceleratingsubstances. 1

The accelerating substances may be of vario types, but the best results have been obtained by the use of reducible compounds and more particularly such compounds which are easily reducible to substances which are capable of being easily reoxidized in the same solution. Typical examples of such compounds are dyestuffs, such as methylene blue or other dyestuffs of the azine type, including oxazine dyes, thiazine dyes, saffranine dyes, diphenyland triphenylmethane dyes, anthraquinone dyes. The property of acceleratlng the reaction between the silver and the dyestufl in the dye destroying agents enumerated above is, however, not only to be found in the case of colored accelerators, but uncolored compounds are also very suitable accelerators. As examples, the following are illustrative of uncolored compounds: dimethylquinoxaline, diamino-phenazine or other quinoxaline or phenazine derivatives. It has beenfoimd that these compounds serve as satisfactory accelerators and when they are substituted in 2,3 positions they are particularly well suited to employ in the reaction. Additional accelerators are disclosed in application Serial No; 179,591, filed December 13, 1937, and United States Letters Patent No. 2,183,395 granted December 12, 1939, to Bela.

The. accelerating effect seems to be a particular property of compounds which are derived irom the general formula:

in 'whichx and Y are oxygen, sulphur, nitrogen,

carbonyl C=O or methylen CH1. T, U, V, W

are hydrogen or sulphonic acid, allryl aryl, NH:, OH or substituted amino or hydroxy groups and instead of T and V and/or V and W cyclic radicals containing these groups may be present.

Furthermore, desensitizing dyestufls or, in some cases, also dyestufls of sensitizing properties can be used. a .In order to show the effect or the new treatin: solutions the following example may .be given. 1

trample A silver halide gelatine layer and a colored lelatine layer in immediate contact therewith are thereby the production of a'well defined picture.

As a yellow dyestufi Chrysophenine G (Schultz 'Farb'stofitabl len', Leipzig 1931, 'Ith edition, volunie 1-, No. 726) and as a magenta dyestufl Tuchechtrot .3 B (manufactured by the Society for Chemical Industry inBasle) for example, may be used-andprecipitated by triphenylguanidine acetate. The light: sensitive material .is exposed in the-usualmanner either with the silver halide present "in the gelatine layer is Iay'erfacingthe light soin'ce or, if the dyestufl intended to act as a filter dyeduring the exposure, from the side of the colored gelatine layer.

with the followingsclutionz V Potassium'bromidel l gra'ms 11.9 r Concentrated sulphuric acild-- ccs.. 27.9 2,3; ethyl,quinoxaline grams 2.0 .W'ater iter-.. 1

for about 10" minutes. The remnant silver is thereafter transformed into a soluble silver salt and leaving only the dyestufl image in the gelatine layer. If in the formula given above the dim'ethyl uuinoxaline is omitted,

' dyestuif'images ofapproxirnately the-same ap- V The 3.5%- thiocarbamide solution is of the followobtained by aminonaphto phenazine;

'p'earance are obtainable only by a prolonged treatmenhflln place of using 2.0 grams of 2,3 dimethylquinoxaline. per liter'treating bath in the above composition; good results have been I ldying 0,1 to 0.5 gram of a phenazi'ne compound/as,the-accelerating agent. Examples ofphenazinefcompounds which may be used-in thismanner are 2,3

diamino-phenazine; 2 amino-phenazine;

2 -oxy-3' amino-phenazine;

(Dibenzo 1'.2' 1.2;

' 1 .2"; 5 .6-J-phenazine) -disu1phonic acid (414"), (cf. Beilstein Suppl. Vol. No. XXV, page 612).

The treating solution used in the above example can be replaced by other treating baths, such as 11% hydrochloricacid or by 3.5% thiocarbamide solution in each-case with the addition of one of the accelerating. substances enumerated above.

ing formula:

'l'hiocarbamidee-e ngrams 3.5 Hydroquin n do 15 Chromium al do 25. Concentrated sulphuricacidm ccs 2.5 2, 3,-dimethyl quinoxaline .grams.. 2.0 wat r in liter 1 The inventioncan be for the production of multicolor images by the simultaneous production of coloredlpart images in a multilayer film c intaining several different silver images and atleast one colored layer in close contact with a silver image-bearing'layer; All of the part images can be'produ'ced in colored gelatine layers adjacent respectively to one of the image-bearing layers or (I -some of the image-bearing layers themselves may After the development' and possibly fixing, the picture is treated reducible dye.

contain the dyestufl for producing therein the part image. Thus, for example, a panchromatic layer is coated onto a support. A gelatine layer dyed with the dye Tuchechtrot 3 B (Schultz Farbostofitabellen, Leipzig 1932, 7th ed., vol. 2,

page 222) is coated over' the panchromatic layer.-

An ortho-chromatic layer dyed with Chlorantinlichtgelb 5 GL (Schultz Farbstoiftabellen, Leipzig 1932, 7th ed., Vol.2, page 48) is coated either directly over the red gelatine layer or over an uncolored thin gelatine intermediate layer. The film described is used as the rear film of a bi-pack, the front film-of which carries an ordinary bluesensitive'sllver halide emulsion layer coated onthe support and a gelatine layer dyed with Chrysophenine G is coated over the bluefsensitive layer. The front film and the rear film are exposed with' the two yellow emulsion layers in contact. After .the exposure, the development and the fixing, the Y dye is destroyed in the yellow gelatine layer of the front film under the influence of the silver image produced in the blue-sensitive silver halide emulsion layer and the reddye in the rear film is destroyed under the influence of the silver image produced in the panchromatic layer, whereas the yellow dye present in the ortho-chromatic layer is destroyed under the influence of the silver image present in this layer. .F'or the dye destruction,

the treating solutions cited above may-be used.

By the local dye destruction a yellow dye image representing the bluecolor selection of the photographic objct is obtained in the front film of the bi-pack, whereas a two-color-image is obtained in the rear film. The-double colored image contains the green color selection in the form of a yellow dye image and the red color selection in the form of a magenta dye image.

I claim: v Y

1. The process of. producing photographic dye images which comprises producing a photographic silver image in a silver halide emulsion layer positioned immediately adjacent to an inactinic colloid layer uniformly dyed with a reducible dye that is resistant totordinary photographic treating solutions and treating both layers in a solution comprising a solvent for silver'salts and a substance-that is rapidly reducible by reducing agents to yield a reduction product that rapidly reduces said reducible dye.

2. The process ofproducingphotographic dye images which comprises producing a photographic silver 'image in a silver halide emulsion layer positioned immediately adjacent to an inactinic colloid layer uniformly dyed with a reducible dye that is resistant to ordinary photographic treating solutions and treating both layers in a solution comprising hydrohaiic acid and a substance thatis rapidly'reducible by reducing agents to yield a reduction product that rapidly reduces said reducible dye.

3. The process of producing photographic dye images which comprises producing a photographic silver image ina silver halide emulsion layer positioned adacent to an inactinic coll'oid layer uniformly dyedwith a reducible dye that is resistant to ordinary photographic .treating solutions and treating both layers in a solution comprising thiocarbamide and a substance that is rapidly reducible by reducing agents; to yield a reduction product that] rapidly reduces said t 4.,I'he process of producing photographic dye images which comprises producing a phi: t0-.

graphic silver imagein a silver halide emulsion layer positioned immediately adJacent to an informula in which X and Y represent a chemical symbol selected from the group of symbols consisting of,

N, S, O, C=O, C=NH, and in which a and b represent a residue selected from the group consisting of H, and four-membered carbon chains forming a condensed ring system,.the substituents being selected from the group of substituentsconsisting of amino groups, oxy groups, alkyl groups, aryl groups and sulphonic groups.

5. The process of producing photographic dye salts and a phen I ecompound.

images which comprises producing a photographic silver image in a silver halide emulsion layer positioned immediately adjacent to an inactinic colloidlayer uniformly dyed with a reducible dye that is resistant to ordinary photographic treating solutions and treating both layers in a solution comprising hydrohalic acid and a reducible organic substance capable of bein rapidly reduced in vsaid solution selected from the group consisting of unsubstituted and substituted compounds of the following general forin which x and Y represent a chemical symbol,

selected from the group of symbols consisting of N, S, O,- C=O, C=NH, and in which man represent a residue selected from the group consisting of H, and four-membered carbonchainsi 6. The process of producing photographic dye images which comprises producing a photo-. graphic silverimage in a silver halide emulsion layer positioned immediately adjacent to an inactinic colloid layer uniformly dyed with areducible dye that is resistant to ordinary photo graphic treating solutions and treating both layers in a solution comprising thiocarbamide and a reducible organic substancecapableof being rapidly reduced in said solution selected from the. group consisting of unsubstituted and substituted compounds of the following general formula in which X and Y represent a chemical symbol.

selected from the group of symbols consisting of N, S O, C=O, C=NH, and in which a and 1) represent a residue selected from the group consisting of H, and four-membered carbon chains forming a condensed ring system, the substituents being selected from the group of substituents consisting of amino groups, oxy groups, al-. kyl groups, aryl groupsand sulph'onic groups.

"I; The process of producing photographic dye images which comprises producing a photo- I graphic silver image in a silver halide emulsion layer positioned immediately adjacent toanin- -,,actinic colloid layer uniformly dyed with areducible dye that isresistantto ordinary photographic treating solutions and treating both laye silver ers in a solution comprising a solvent-for 8. The process of producing photographic dye images which comprises producing a photographic sllver image in asilver halide emulsion layer positioned immediately adjacent to an inactinic .colloid layer uniformly dyed with a reducible dye that is resistant to. ordinary photographic treating solutions and treating both layers in a solution comprising asolvent for silver saltsand a-quinoxaline compound.

9. The process of producingphotographic dye images which comprises producing ,a ;photo-. graphic silver image in a silver halide emulsion layer positioned immediately adjacentto aninactiniccolloid layer uniformly dyed with a reducible dye that is resistant to ordinary photographic treating solutions and treating both layers in a solution comprising .thiocarbamide and aphenazine compound. v g 10. The process of producing photographic dye images which "comprises 1 producing a photographic silver image in a. silver halide emulsioni layer "positioned immediately adjacent to an inactiniccolloid layer uniformly dyed with a reducible dye that is resistant to ordinary photographic treating solutions and treating both lay- .ersin a solution comprising hydrohalic acidan'd a quinoxaline compound; Y

11. 'The process of producing. photographic dye images which comprises producing ..a photographic silver image in a silver halide emulsion layer positioned immediately adjacent to an in-' actinic colloid layer uniformly dyed with a reducible dye that is resistant to ordinary photo graphic treating solutions and treating both layersin a solutioncomprising thiocarbamide and I a quinoxaline compound.

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